1245821 五、發明說明（1) 【技術領域】 本發明係相關於加工工程性、芯鞘的耐層離性、染色 物的向紅性等優異之複合纖維。 【背景技術】 通常，聚丙烯和聚乙烯等聚烯類樹脂較便宜且具有優 異的力學性能，因此廣泛地應用在纖維用途。 惟從染色性、耐熱性等觀點受限制的用途’例如主要 應用在非衣料用途。改善聚烯類纖維的染色性雖可混煉 顏料，惟會有工程性、品質大幅降低等問題。 另一方面，聚對苯二甲酸乙二醇酯和聚對苯二甲酸丁 二醇酯等聚酯類樹脂其染色性耐熱性等優異，又聚醯胺 的物理特性優異，因此廣泛應用在纖維用途，惟會有比 重較大等問題。 又，聚烯類纖維和聚酯類纖維均爲疏水性，會有纖維 的吸水性、吸濕性較差等缺點。爲要改善這些缺點，從 以前便進行各種改良方法，例如聚酯等疏水性聚合物和 含有羥基之聚合物進行複合紡絲，藉此使疏水性纖維具 有親水性等性能。 具體而言，特公昭5 6- 5 846號和特公昭5 5 - 1 3 72號公 報等揭示聚酯、聚丙烯、聚醯胺等疏水性熱塑性樹脂和 乙烯-乙烯醇類共聚物之複合纖維。 惟上述的複合纖維中，進行複合的二聚合物間之界面 因黏合性小，二成份易發生層離，在使用目的上易造成 困擾。特別是進行相對於強拈加工和假拈加工等纖維的 1245821 五、發明說明（4) 各種添加劑。 另一方面，使用於鞘成份B的其他熱塑性聚合物，主 要爲和芯成份A非相溶性的聚合物，例如可使用聚烯類 樹脂、聚酯類樹脂、聚醯胺類樹脂、聚丙烯酸類樹脂、 醋酸乙烯類樹脂、二烯類樹脂、聚胺甲酸類樹脂、聚碳 酸酯樹脂、聚芳基酯、聚苯撐硫化物、聚醚酯酮、氟加 工樹脂、半芳香族聚酯醯胺、乙烯-乙烯醇類共聚物等聚 合物。 又，和芯成分A相同，在不破壞本發明效果的範圍內 ，鞘成分B亦可含有氧化鈦、二氧化矽、氧化鋇等無機 物、碳黑、染料和顏料等著色劑、抗氧化劑、紫外線吸 收劑、光穩定劑等各種添加劑。 本發明中構成芯鞘型複合纖維的芯成分A和鞘成分B 的組合無特別的限制，惟以本發明般特異的型態進行複 合成分間的界面結構，藉此使用的熱塑性聚合物進行組 合時其S P値（S ο 1 u b i 1 i t y P a r a m e t e 1.;溶解指數）的差即使 大於〇 · 5、更且大於1 · 〇、特別是大於i . 8，耐層離性的 改善效果仍明顯。 又’本發明中爲要使複合纖維具有良好的親水性和天 然纖維般外觀、優異的發色性、光澤，較理想的鞘成分 B係使用乙烯-乙烯醇類共聚物。 乙_ -乙烯醇類共聚物係由乙烯-醋酸乙烯共聚物進行 島化而彳守，巷化度9 5 %以上的高巷化度者較理想，通常 使用乙烯共聚比例爲25〜70莫耳％者，亦即乙烯醇成分 1245821 五、發明說明（5) (包含未皂化醋酸乙烯成分和縮醛化乙烯醇成分等）約佔 30〜75莫耳％者。 聚合物中的乙烯醇成分的比例若低，因羥基減少而降 低親水性等特性，無法製得目的具良好親水性的天然纖 維般外觀。相反地，若乙烯醇成分的比例過多，熔融成 形性低落和芯成份A進行複合紡絲時造成牽絲性不佳， 進行紡絲時或延展時發生單絲斷裂、斷絲等現象。 因此，爲要製造本發明的目的纖維，以高皂化度且乙 烯共聚比例爲25〜70莫耳％者較適用。 使用鞘成分B和作爲複合的芯成分A的聚酯等高熔點 聚合物時，爲要長時間穩定且連續地紡絲，較理想者爲 提高鞘成分B熔融成形時的耐熱性，惟適當地設定乙烯 的共聚比例之範圍和使聚合物中金屬離子的含量小於規 定量等亦能達到效果。 鞘成分B的熱分解機制可大略分爲2種，一爲聚合 物-主鏈間發生交聯反應形成皂化物，另一爲包括側鍊 分離等的分解機制的情形，除去鞘成分B中的金屬離子 可大幅提高熔融紡絲時的熱安定性。特別是Na+，K +離 子等第I族的鹼金屬離子和CA2+，Mg2 +離子等第II族 的鹼土類金屬離子含量均小於100 ppm時具有顯著的效 果。 特別是長時間連續地在高溫條件下進行熔融紡絲時， 若鞘成分B中發生凝膠物，此凝膠物會慢慢地阻塞、堆 積在紡絲過濾器上，結果使紡絲組件壓力急速上升而噴 1245821 五、發明說明（6) 嘴壽命變短，同時紡絲時頻頻發生單絲斷裂、斷絲等情 形。凝膠物的堆積若繼續進行會阻塞聚合物配管並引起 不良狀況較不理想。 藉著去除鞘成分B中的第I族鹼金屬離子、第Π族鹼 土金屬離子，即使在高溫下特別是高於2 5 (TC長時間連 續地進行熔融紡絲時，亦不易因發生凝膠物而引發不良 狀況。 因此，這些金屬離子的含量均小於5 0 ppm較理想， 又以小於1 〇 ρ ρ πι者更佳。 乙烯-乙烯醇類共聚物的製法舉其中一例說明，例如 在甲醇等聚合溶劑中使乙烯和醋酸乙烯在自由基聚合觸 媒下進行自由基聚合，其次去除未反應的單體，藉由鹼 性蘇打引發皂化反應，形成乙烯-乙烯醇類共聚物後在 水中顆粒化，進行水洗並乾燥。之後的工程中無論如何 都容易使聚合物中有鹼金屬和鹼土類金屬，通常混有數 百ppm以上的驗金屬、驗土類金屬。 盡量減少驗金屬離子及鹼土類金屬離子的含量之方法 ，例如聚合物的製造工程中皂化處理後進行顆粒化後， 以大量的含有醋酸的純水溶液淸洗濕潤狀態的顆粒’再 以大量、過剩的純水淸洗顆粒後即可製得。 又，以鹼性蘇打使乙烯和醋酸乙烯的共聚物皂化可製 得鞘成分B，其皂化度在95°/。以上較理想。鹼化度若降 低聚合物的結晶性會低落’不僅強度等纖維物性會低落 ，鞘成分B亦容易軟化’除了在加工工程中會發生不良 1245821 五、發明說明（7) 狀況，同時製得的纖維結構物的外觀、觸感均會變差。 本發明中使用乙烯-乙烯醇類共聚物作爲鞘成分B時 ’芯成分A使用的聚合物以熔點大於i6(rc較適當，又 以大於1 8 0。(：的熱塑性聚合物更理想，例如以尼龍1 2、 尼龍6、尼龍66爲代表的聚醯胺、以聚丙烯爲代表的聚 烯、以聚對苯二甲酸三甲二醇酯爲代表的聚酯等較適當 。亦可使用聚對苯二甲酸六甲二醇酯、聚乳酸等聚酯。 特別是聚對苯二甲酸烯烴酯類聚酯中，部分的對苯二 甲酸成分亦可被其他二羧酸成分取代，至於二醇成分， 除了主要的二醇成分之外，亦可被少量其他的二醇成分 取代。 對苯二甲酸之外的二羧酸成分例如間苯二甲酸、萘二 羧酸、二苯二羧酸、二苯氧基二乙烷二羧酸、Θ —羧基乙 氧基苯甲酸、對殘基苯甲酸、己二酸、癸二酸、1,4 -環 己烷二羧酸等。 又，二醇成分例如乙二醇、三甲二醇、四甲二醇、六 甲二醇、二乙二醇、新戊二醇、環己烷-丨，4_二甲醇、聚 乙二醇、聚四甲二醇、雙苯酚A、雙苯酚s等。 特別是將下列一般式（i)表示的化合物共聚合對提昇耐 層離性甚有助益。 X 1 — D — X 2 ( i )1245821 V. Description of the invention (1) [Technical field] The present invention relates to a composite fiber having excellent processability, resistance to delamination of a core sheath, and redness of a dyed substance. [Background Art] Generally, polyolefin resins such as polypropylene and polyethylene are relatively inexpensive and have excellent mechanical properties, and therefore they are widely used in fiber applications. However, applications that are restricted from the viewpoints of dyeability and heat resistance, for example, are mainly used for non-clothing applications. Although pigments can be kneaded to improve the dyeability of polyolefin fibers, there are problems such as engineering and a significant decrease in quality. On the other hand, polyester resins such as polyethylene terephthalate and polybutylene terephthalate are widely used in fibers because they have excellent dyeing, heat resistance, and other physical properties. Use, but there will be problems such as a larger proportion. In addition, both polyolefin-based fibers and polyester-based fibers are hydrophobic, and they have disadvantages such as poor water absorption and hygroscopicity. To improve these disadvantages, various improvements have been made in the past, such as composite spinning of a hydrophobic polymer such as polyester and a polymer containing a hydroxyl group, thereby making the hydrophobic fiber hydrophilic and other properties. Specifically, Japanese Unexamined Patent Publication No. 5 6- 5 846 and Japanese Unexamined Patent Publication No. 5 5-1 3 72 disclose composite fibers of hydrophobic thermoplastic resins such as polyester, polypropylene, and polyamide, and ethylene-vinyl alcohol copolymers. . However, in the above-mentioned composite fibers, the interface between the two polymers to be combined is small, and the two components are prone to delamination, which is likely to cause problems in the use purpose. In particular, 1245821 is used for fibers such as strong reed processing and false reed processing. 5. Description of the invention (4) Various additives. On the other hand, other thermoplastic polymers used in sheath component B are mainly polymers that are not compatible with core component A. For example, polyolefin resins, polyester resins, polyamide resins, and polyacrylic resins can be used. Resin, vinyl acetate resin, diene resin, polyurethane resin, polycarbonate resin, polyarylate, polyphenylene sulfide, polyetherester ketone, fluorine processing resin, semi-aromatic polyester amide And polymers such as ethylene-vinyl alcohol copolymers. Also, as with the core component A, the sheath component B may contain inorganic substances such as titanium oxide, silicon dioxide, and barium oxide, colorants such as carbon black, dyes, and pigments, antioxidants, and ultraviolet rays, as long as the effects of the present invention are not impaired. Various additives such as absorbents and light stabilizers. In the present invention, the combination of the core component A and the sheath component B constituting the core-sheath composite fiber is not particularly limited, but the interface structure between the composite components is performed in a specific form like the present invention, and the thermoplastic polymer used thereby is combined When the difference in SP 値 (S ο 1 ubi 1 ity Paramete 1 .; solubility index) is greater than 0.5, more than 1 · 〇, especially greater than i. 8, the effect of improving delamination resistance is still obvious. . In addition, in the present invention, in order to provide the composite fiber with good hydrophilicity and natural fiber-like appearance, excellent color development, and gloss, the preferred sheath component B is an ethylene-vinyl alcohol copolymer. Ethylene-vinyl alcohol copolymers are islanded and protected by ethylene-vinyl acetate copolymers. Those with a high degree of lanewayization above 95% are ideal. Usually, the copolymerization ratio of ethylene is 25 ~ 70 moles. %, Namely vinyl alcohol component 1245821 V. Description of the invention (5) (including unsaponified vinyl acetate component and acetalized vinyl alcohol component, etc.) account for about 30 to 75 mole%. If the proportion of the vinyl alcohol component in the polymer is low, characteristics such as a decrease in the hydrophilicity due to a decrease in the hydroxyl group, and the like cannot be obtained with the objective natural fiber-like appearance with good hydrophilicity. Conversely, if the proportion of the vinyl alcohol component is too large, the melt formability is low and the core component A has poor spinning properties during composite spinning, and monofilament breakage or filament breakage occurs during spinning or stretching. Therefore, in order to produce the target fiber of the present invention, a high degree of saponification and an ethylene copolymerization ratio of 25 to 70 mol% are more suitable. In the case of using a high melting point polymer such as sheath component B and polyester as a composite core component A, in order to stably and continuously spin for a long period of time, it is desirable to increase the heat resistance during melt molding of the sheath component B. The effect can also be achieved by setting the range of the copolymerization ratio of ethylene and making the content of metal ions in the polymer smaller than a predetermined amount. The thermal decomposition mechanism of sheath component B can be roughly divided into two types. One is the formation of saponification by cross-linking reaction between polymer and main chain, and the other is the case of decomposition mechanism including side chain separation. Metal ions can greatly improve thermal stability during melt spinning. In particular, Group I alkali metal ions such as Na +, K + ions and Group II alkaline earth metal ions such as CA2 + and Mg2 + ions all have significant effects. In particular, when melt spinning is continuously performed under high temperature conditions for a long time, if a gel substance is generated in the sheath component B, this gel substance will slowly block and accumulate on the spinning filter, resulting in pressure on the spinning assembly. Rapidly rising and spraying 1245821 V. Description of the invention (6) The life of the nozzle is shortened, and at the same time, the filament breaks and breaks frequently during spinning. If gelation continues, it is not preferable to block polymer piping and cause undesirable conditions. By removing the Group I alkali metal ions and Group Π alkaline earth metal ions in the sheath component B, even at high temperatures, especially above 2 5 (TC, continuous melt spinning for a long time, it is difficult to cause gelation. Therefore, the content of these metal ions is preferably less than 50 ppm, and it is more preferable to use less than 10 ρ ρ π π. One example of the preparation method of ethylene-vinyl alcohol copolymer, for example, in methanol In a polymerization solvent, ethylene and vinyl acetate are radically polymerized under a radical polymerization catalyst, followed by removal of unreacted monomers, and the saponification reaction is initiated by alkaline soda to form ethylene-vinyl alcohol copolymer particles in water. It is easy to make alkaline metals and alkaline earth metals in the polymer in the subsequent projects, and it is usually mixed with hundreds of ppm or more of metal inspection and soil inspection metals. Minimize metal inspection ions and alkaline earth A method for the content of metalloid ions, for example, after saponification treatment in a polymer manufacturing process and granulation, washing a wet state with a large amount of a pure aqueous solution containing acetic acid The granules can be prepared by washing the granules with a large amount of excess pure water. In addition, saponification of the copolymer of ethylene and vinyl acetate with alkaline soda can produce sheath component B, which has a degree of saponification of 95 ° /. The above is ideal. If the degree of alkalinity is lowered, the crystallinity of the polymer will be lowered. "Not only the physical properties of the fibers such as strength will be lowered, but the sheath component B will also be easily softened." In addition to the defects in the processing process, 1245821 V. Description of the invention (7) At the same time, the appearance and feel of the fiber structure obtained at the same time will be deteriorated. When the ethylene-vinyl alcohol copolymer is used as the sheath component B in the present invention, the polymer used in the core component A has a melting point greater than i6 (rc is more appropriate, Also more than 1 8 0. (: thermoplastic polymers are more ideal, for example, polyamide 1 represented by nylon 1, 2, nylon 6, nylon 66, polyolefin represented by polypropylene, polytrimethylene terephthalate Polyesters such as glycol esters are suitable. Polyesters such as poly (hexamethylene glycol terephthalate) and polylactic acid can also be used. In particular, some of the terephthalic acid in poly (ethylene terephthalate) polyesters Formic acid can also be used by other dicarboxylic acids Substituting, as for the diol component, in addition to the main diol component, a small amount of other diol components may also be substituted. Dicarboxylic acid components other than terephthalic acid such as isophthalic acid, naphthalenedicarboxylic acid, Diphenyldicarboxylic acid, diphenoxydiethanedicarboxylic acid, Θ-carboxyethoxybenzoic acid, p-residual benzoic acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid Examples of the diol component include ethylene glycol, trimethyl glycol, tetramethyl glycol, hexamethyl glycol, diethylene glycol, neopentyl glycol, cyclohexane, 4-dimethanol, and polyethylene glycol. , Polytetramethylene glycol, bisphenol A, bisphenols, etc. In particular, the copolymerization of the compound represented by the following general formula (i) is very helpful to improve the resistance to delamination. X 1 — D — X 2 (i )
I S Ο , Μ (惟’ D表不爲3價的芳香族基，χ i及χ 2表示爲相 1245821 五、發明說明（8 ) 同或相異之酯形成性官能基或氫原子，Μ爲鹼金屬、鹼 土類金屬、烷基鳞等。） 從聚合時的耐熱性之觀點考量，芯成分Α的共聚成分 亦即上述化合物（i )，其中的D爲3價的芳香族基較理想 。例如1，3,5 -苯三基、1，2,3 -苯三基、1，3,4 -苯三基等苯 三基，1，3,6-萘三基、1，3,7·萘三基、I,4,5-萘三基、 1,4,6-萘三基等萘三基等。 Μ爲鈉、鉀、鏗等鹼金屬原子、鈣、鎂等鹼土類金屬 原子或四正丁膦基、丁基三苯膦基、乙基丁膦基等烷基 膦基。 X 1及Χ2表示爲酯形成性宮能基或氫原子，可爲相同 或相異。在聚合物的主鏈中，從共聚的觀點考量以酯形 成性官能基較理想。具體的酯形成性官能基，例如有下 列的官能基。 R I CMN o I 〇 Η ο I CMn ο R 〇 I CMN ο (CH2)a—〇H、一 C 一 [〇（CH2)b]d — 〇H、IS Ο, Μ (but 'D means not a trivalent aromatic group, χ i and χ 2 are expressed as phase 1245821 V. Description of the invention (8) Identical or different ester-forming functional group or hydrogen atom, M is Alkali metals, alkaline earth metals, alkyl scales, etc.) From the viewpoint of heat resistance during polymerization, the copolymerization component of the core component A, that is, the above-mentioned compound (i), in which D is a trivalent aromatic group, is preferred. For example, benzenetriyl such as 1,3,5-benzenetriyl, 1,2,3-benzenetriyl, 1,3,4-benzenetriyl, 1,3,6-naphthalenetriyl, 1,3,7 Naphthalenetriyl, naphthalenetriyl, 1,4,5-naphthalenetriyl, 1,4,6-naphthalenetriyl, etc. M is an alkali metal atom such as sodium, potassium, and osmium; an alkaline earth metal atom such as calcium or magnesium; or an alkylphosphine group such as tetra-n-butylphosphino, butyltriphenylphosphino, and ethylbutylphosphino. X 1 and X 2 are represented by an ester-forming hornyl group or a hydrogen atom, and may be the same or different. In the main chain of the polymer, it is desirable to use an ester-forming functional group from the viewpoint of copolymerization. Specific ester-forming functional groups include, for example, the following functional groups. R I CMN o I 〇 Η ο I CMn ο R 〇 I CMN ο (CH2) a—〇H, —C— [〇 (CH2) b] d — 〇H,
一〇 一（CH2)b — [〇（CH2)b]d — 〇H (惟，R表示爲低級烷基或苯基、a及d係大於1的整 數、b係大於2的整數。） 化合物（i)的具體例例如5-硫代間苯二甲酸鈉、5-硫代 間苯二甲酸鉀、5-四丁基鐵硫代間苯二甲酸、2,6-二羧 -1 0 - 1245821 五、發明說明（1〇) 狀況，不易使鄰接的突出部分間隔小於1 .5 /z m，有時亦 無法充分發揮染色時的向紅性。 又突出部分和扁平切面芯成分如第1，2圖般排列時 可充分地對抗來自所有方向的外力。 又，在第2圖的纖維切面，各個芯成分A的形狀其中 最長徑（L)/最短徑（D)大於1.5，又以大於2的扁平形狀 較理想。 在本發明上述說明的第1圖及第2圖的任一複合型態 中，芯成分A的鄰接褶狀突出部分之間格或鄰接扁平切 面芯成分的間隔（I)小於1.5// m，此突出部分或扁平切 面芯成分的任一長軸相對於纖維切面外圍以90°± 15° 的角度排列很重要。芯成分A的鄰接突出部分間隔或鄰 接扁平切面芯成分的間隔（I)若超過1.5/zm，進行染色 處理時的向紅性和均染性不足。又，延長突出部分或扁 平切面芯成分的長軸時，和纖維切面外圍的角度（R)小於 75°排列時或大於105°排列時，作用在纖維的外力易 使芯成分A和鞘成分B的界面發生層離，伴隨發生染色 物的白化現象較不理想。 從以上的觀點，本發明中鄰接的突出部分間隔或鄰接 的扁平切面芯成分的間隔（I)小於1.2// m較理想，此突 出部分或扁平切面芯成分的任一長軸相對於纖維切面外 圍以90415°的角度排列者較理想。 又，此處所謂鄰接突出部分的間隔或鄰接扁平切面芯 成分的間隔（I)係指鄰接的各個突出部分前端間的平均間 -12- 1245821 五、發明說明（11) 隔，或鄰接的各個扁平切面芯成分的長軸方向的前端 (纖維外圍附近的前端部分）間的平均間隔，在不影響本 發明效果的範圍內多數突出部分間隔、芯成分間隔中， 部分超過1 · 5 // m的間隔可存在部分的纖維切面。 本發明中更重要的部分係芯成分A的外周長（L2)和複 合纖維的外周長（L〇的比符合下列（1)式表示的內容。 2 ^ X/C (1) X ;芯成分A的外周長和複合纖維的外周長的比（L2/L!) C ;以全體複合纖維爲1時，芯成分A的質量複合比率 芯成分A的外周長（L2)和複合纖維的外周長（LQ的比 X，隨芯成分A的複合比率而變化，惟X/C大於2，較 理想爲2.5倍以上，又以3倍以上更佳，特別以5倍以 上最理想。X/C小於2時，因無法充分地發現界面的層 離效果較不適用。 本發明中防止界面層離效果的作用機制目前尙未完全 淸楚，惟可推論係因複合成分的黏著面積增大以及由芯 成分A形成的突出部分的固定效果之相乘效果所產生的 作用。 較理想的鞘成分B和芯成分A的複合比率爲90 : 1 0 〜10 : 90(質量比率），又以70 : 3 0〜3 0 : 70特別理想， 可依各個的複合型態和纖維切面形狀作適當的設定。 鞘成分B的複合比率小於1 〇質量％時，因芯成分A 的表面暴露等問題使品質低落，又，失去鞘成分B的聚 -13- 1245821 五、發明說明（12) 合物特性。另一方面，鞘成分B的複合比率超過1 0質 量％之複合纖維，因失去芯成分A的聚合物特性較不理想。 本發明中，例如使用易染性的聚合物作爲芯成分A， 使芯成分A的突出部分的間隔小於1 · 5 // m，使用易染 性的聚合物，使用低折射率的乙烯-乙烯醇類共聚物作 爲鞘成分B，藉此可具有鮮明的發色性、向紅性等。 這些纖維使用在運動服材料時不僅需具有發色性，亦 要求具有光澤，通常具有光澤的纖維其發色性差，相反 地，若具有發色性則不易同時具有光澤。針對於此，本 發明將複合成分和切面形狀作成特定的物質，藉此可製 得具有鮮明發色性及光澤的纖維。爲要使其具有光澤， 具有愈多光反射的平坦面較理想，或維持具有輕微異形 度的平坦面之切面形狀較有效。這類的切面例如三角或 扁平切面的纖維最理想。 本發明中纖維的粗度無特別的限制可爲任一粗度，惟 爲要製得發色性、光澤感、外觀、觸感優異的纖維，複 合纖維的纖維纖度爲〇·3〜11 dtex較理想。又，不僅是長 纖維短纖維亦可具有本發明的效果。 本發明複合纖維的製法無特別的限制，只要能製得符 合本發明的規定之複合纖維即可，使用複合紡絲裝置， 將鞘成分B和芯成分A聚合物的複合流導入噴嘴導入口 時，芯成分A從圓周上設有和芯成分A形成突出部分的 個數相同數目的細孔之分流板通過，以鞘成分B覆蓋從 各個細孔通過的全部芯成分A，同時向著噴嘴導入口的 中心導入複合流，藉著紡絲噴嘴使其熔融吐出即可進行 -14- 1245821 五、發明說明（13) 製造。此時若在分流板中間設置細孔，可製得如第2圖 所示之複合切面的纖維，中間不設置細孔時可製得如第 1圖所示之複合切面的纖維。 紡絲·延展的方法例如有以低速、中速熔融紡絲後進 行延展之方法，以高速直接紡絲延展法，紡絲後同時或 接著進行延展和假拈等方法，可採用任一種方法。 又，本發明中使芯成分A含有無機微粒較理想，此時 ，較理想的無機微粒的一次平均粒徑爲0.01〜5.0 // m， 又以0· 03〜3.0// m更佳。若無機微粒的一次平均粒徑小 於0 · 0 1 μ m，爲要進行延展的加熱區域的溫度和絲線的 運轉速度、運轉絲線相關的張力等只要產生些微變動， 複合纖維會發生捲毛、絨毛、纖度斑點等。另一方面， 若無機微粒的一次平均粒徑超過3.0 // m，纖維的延展性 低落導致製絲性不佳，製造複合纖維時會發生斷絲等現 象。此處，無機微粒的一次平均粒徑係指以離心沉澱法 進行測定時的値。 較理想的無機微粒約含量爲芯成分A的〇 . 0 5〜1 0 · 0質 量％ ’又以〇 . 3〜5.0質量％更佳。若無機微粒約含量少於 〇. 1質量％，爲要進行延展的加熱區域的溫度和絲線的運 轉速度、運轉絲線相關的張力等只要產生些微變動，製 得的複合纖維會發生捲毛、絨毛、纖度斑點等，另一方 面’若無機微粒約含量超過10.0質量。/。，在纖維的展延 工程中無機微粒會過度產生運轉絲線和空氣間的阻力， 發生捲毛、斷絲等現象使工程不穩定。 又，本發明的芯成分A中，無機微粒的一次平均粒徑（"m) -15- 1245821 五、發明說明（14) 和聚合物中的含量（質量％)之積（Y)能符合0·01 s 3.0 者較理想。若積Υ小於〇.〇 1，複合纖維會發生捲毛和絨 毛、纖度斑點等，工程性不佳較不理想，纖維中多產生 未延展部分則不易使用在衣料用途。若積Υ超過3.0， 纖維化工程中易發生捲毛、斷絲等現象工程性不佳。 無機微粒的種類不拘，只要對形成纖維的聚酯沒有劣化 作用且本身穩定性佳的無機微粒皆可使用。本發明中可 有效地使用的無機微粒之代表例有二氧化矽、氧化鋁、 碳酸鈣、氧化鈦、硫酸鋇等，這些無機微粒可單獨使用 或2種以上混合使用。2種以上混合使用時，各個無機 微粒的粒徑（al，a2,…an)和含量（bl，b2,…bn)之積的和必 須符合上述範圍。亦即，Y = alxbl+a2xb2+ .·ιηχΐ3η 的Υ必須符合上述範圍。 無機微粒加入芯成分Α中的方法無特別的限制，在熔 融紡出芯成分A前的任一階段，將無機微粒均勻地混合 再添加、混合在芯成分A中即可。例如在芯成分a的聚 合過程中之任一時點添加無機微粒，或在聚縮合結束後 製造顆粒等之後添加無機微粒，或從紡絲抽絲頭紡出芯 成分A前的階段，使無機微粒均勻熔融混合等方法皆可。 由以上方法製得的本發明的纖維可作爲各種纖維聚集 體（纖維結構物）使用。此處所謂纖維聚集體，可爲由本 發明的纖維單獨構成的織物、不織布，亦可爲部分使用 本發明的纖維所構成的織物、不織布，例如天然纖維、 化學纖維、合成纖維等，作爲和其他纖維形成的交互織 布、或混紡線、混纖線使用的織物、混綿不織布等，本 -16- 1245821 五、發明說明（15) 發明纖維在這類織物和不織布中所佔的比例大於1 〇質 量％，又以大於3 0質量％者較理想。 本發明的纖維的主要用途，單獨或一部份使用長纖維 作成織物，可作爲具有良好外觀、觸感的衣料用素材。 另一方面，短纖維的用途有衣料用纖維、乾式不織布、 及濕式不織布等，不僅衣料用途亦適用於各種生活材料 、產業材料等非衣料用途。 【實例】 下列以實例更具體地說明本發明，惟本發明不受限於 這些實例。 聚合物的固有黏度： 使用苯酚和四氯乙烷的等質量混合溶劑，在30°C恆溫 槽中使用、烏比羅德（音譯）型黏度劑測定聚酯的固有黏 度。使用85 %苯酚在30°C測定乙烯-醋酸乙烯共聚物的 皂化物的固有黏度。 發色鮮明性及光澤性： 1 〇位品評員對以一定的染色條件染色的布料進行官能 評估。其結果非常優異爲2點，優異爲1點，不良爲〇點。 〇：總計點數大於1 5點 △:總計點數爲8〜14點 X :總計點數小於7點 複合纖維的各聚合物之黏合性： 將2 4〜36的纖維作成500- 1 000 T/m的撚絲，在此狀 態下切斷絲線，以電子顯微鏡放大5 0 〇倍觀察切斷面的 纖維的層離狀態。切斷點爲1 0處，以下述的基準進行 -17- 1245821 五、發明說明（16) 評估。 ◎:層離程度小於1成 〇：層離程度爲1成〜2成 △:層離程度爲2成〜5成 X :層離程度大於5成 纖維強度：以JISL 1013爲基準進行測定。 纖維化工程性：評估每1噸的絨毛數·斷絲數。 ◎:絨毛·斷絲數合計小於1個/噸 〇：絨毛·斷絲數合計爲1〜2個/噸 △:絨毛·斷絲數合計爲2〜5個/噸 X :大於5個/噸 染色性··以下述的條件求筒編素材進行染色時的染色率 Foron Navy S2GL 2% omf Di sper-TL 1 g /1 醋酸（5 0%) 1 cc /1 液比 1:50 120°C x40 分鐘 總合評估：總括地觀察纖維化工程性、耐層離性、染色 性等項目，以下基準進行評估。 ◎:各項目均爲◎時 〇：各項目均爲〇時 X及△〜X表示爲和各項目中最差的評估結果同等。 實例1 使用尼龍6(8?値=12.7，宇部興產股份公司製101381〇) 作爲鞘成分B，使用聚對苯二甲酸乙二醇酯（SP値=10.7 -18- 1245821 五、發明說明（2〇 ) 皂化度9 9 °/。以上的乙烯-醋酸乙烯共聚物皂化物後，以 含有少量醋酸之過量的純水重覆淸洗後，再使用過量的 純水重覆淸洗，使聚合物中的鉀、鈉離子及鎂、鈣離子 的含量均小於1 0 ppm，之後使用脫水機分離出聚合物中 的水分後，再以低於1 0 (TC的溫度充分地進行真空乾燥 ，製得固有黏度[η] = 1 .05 dl/g的聚合物（SP値=17.2)， 將此聚合物作爲鞘成分B用的聚合物。 另一方面，使用四異丙基鈦酸鹽作爲聚合觸媒並加入 聚對苯二甲酸丁二醇酯（由佔全酸成分的1 . 7莫耳。/。的5 -硫代間苯二甲酸鈉經過共聚形成），使聚合物中鈦金屬 原子含量爲35 ppm，以常法進行聚合，製得固有黏度 [η] = 0.85 dl/g的聚合物，作爲芯成分A用的聚合物。 在鞘成分B和芯成分A的複合比率（質量比率）50 : 50 的條件，以紡絲溫度26(TC、捲取速度3 500 m/分的條 件進行熔融複合紡絲，製得如第3圖所示切面形狀的複 合纖維（8 3 dtex/24纖維）。此複合纖維的芯成分a的突 出部分有5 0個，鄰接突出部分間的平均間隔爲〇 . 3 5 // m 。芯成分A的外周長（L2)和複合纖維的外周長（Ld的比 ί2/Ι^ = 4·5(Χ/(： = 9·0)，強度爲 3.1 N/dtex。其次進行 800 T/Μ的實拈，製作織物，使用一般的液流染色機以下列 表示的交聯處理條件及染色條件使製得的織物進行染色 ，之後以常法進行乾燥完成工程。染色後的織物具有良 好的發色、鮮明性及優異的光澤感，完全不發生芯鞘界 面層離現象。且具有良好的外觀、觸感。結果如表4所 -22- 1245821 五、發明說明（21) 示。 交聯處理條件 處理劑：1,1,9,9，-雙乙二羥基壬烷 10% omf 十二苯磺酸鈉 0.5g/l 馬來酸 lg/1 液比：1 : 5 0 溫度：115°C x40分鐘 染色條件 染料：Dianix Red BN-SE(CI Disperse Red 127) 分散助劑：DisperTL(明成化學工業公司製） PH調節劑：硫酸銨 醋酸（48%) 液比：1 : 5 0 溫度：115°C x40分鐘 還原淸洗 氫化亞硫酸氫鹽 lg/1 阿米拉金（第一工業製藥） lg/1 NaOH lg/1 液比：1 : 3 0 溫度：80°C xl20分鐘 5 % omf lg/1 lg/1 lg/1 -23- 1245821 五、發明說明（22)表3101 (CH2) b — [〇 (CH2) b] d — OH (However, R is a lower alkyl or phenyl group, a and d are integers greater than 1, and b is an integer greater than 2.) Compound Specific examples of (i) include, for example, sodium 5-thioisophthalate, potassium 5-thioisophthalate, 5-tetrabutyl iron thioisophthalate, and 2,6-dicarboxyl-1 0-1245821. 5. Description of the invention (10) In the situation, it is difficult to make the interval between adjacent protruding parts smaller than 1.5 / zm, and sometimes the reddishness during dyeing cannot be fully exerted. When the protruding parts and the flat cut core components are arranged as shown in Figs. 1 and 2, they can sufficiently resist external forces from all directions. In the cross section of the fiber in Fig. 2, the shape of each core component A is preferably a flat shape having a longest diameter (L) / shortest diameter (D) of more than 1.5 and more than 2. In any one of the first and second figures of the above description of the present invention, the interval (I) between the adjacent pleated protruding portions of the core component A or the adjacent flat cut surface core component is less than 1.5 // m, It is important that any major axis of this protruding portion or flat cut core component is aligned at an angle of 90 ° ± 15 ° with respect to the periphery of the fiber cut surface. If the interval between the adjacent protruding portions of the core component A or the interval (I) adjacent to the flat-cut core component exceeds 1.5 / zm, the redness and leveling properties when dyeing are insufficient. In addition, when the long axis of the protruding component or the flat cut core component is extended, when the angle (R) with the periphery of the fiber cut surface is less than 75 ° or when the angle is greater than 105 °, the external force acting on the fiber tends to make the core component A and sheath component B Delamination occurs at the interface, and the whitening phenomenon of the dyed material is not ideal. From the above point of view, in the present invention, the interval between adjacent protruding portions or the interval between adjacent flat cut core components (I) is preferably less than 1.2 // m, and any major axis of this protruding portion or flat cut core component is relative to the fiber cut surface. It is ideal to arrange the periphery at an angle of 90415 °. Here, the interval adjacent to the protruding portion or the interval adjacent to the flat-cut core component (I) refers to the average interval between the tips of the adjacent protruding portions -12-1245821. V. Description of the Invention (11) The interval, or each adjacent portion The average interval between the front ends of the flat-cut core components in the major axis direction (front end portions near the periphery of the fiber), most of the interval between the protruding portions and the interval between the core components within a range that does not affect the effect of the invention, exceeds 1 · 5 // m There may be part of the fiber section. The more important part of the present invention is the ratio of the outer perimeter (L2) of the core component A and the outer perimeter (L0) of the composite fiber to the content represented by the following formula (1). 2 ^ X / C (1) X; core component The ratio of the outer perimeter of A to the outer perimeter of the composite fiber (L2 / L!) C; when the total composite fiber is 1, the mass composite ratio of the core component A is the outer perimeter (L2) of the core component A and the outer perimeter of the composite fiber (The ratio X of LQ varies with the composite ratio of core component A, but X / C is greater than 2, more preferably 2.5 times or more, more preferably 3 times or more, and especially 5 times or more is most desirable. X / C is less than At 2 o'clock, the delamination effect at the interface cannot be fully found, which is not applicable. The mechanism of preventing the delamination effect at the interface in the present invention is not fully understood at present, but it can be inferred that the adhesion area of the composite component increases and the core The effect of the multiplication effect of the fixing effect of the protruding part formed by component A. The ideal composite ratio of sheath component B and core component A is 90:10 to 10:90 (mass ratio), and 70: 3 0 ~ 3 0: 70 is particularly ideal, and can be appropriately set according to each composite type and fiber cut shape When the composite ratio of the sheath component B is less than 10% by mass, the quality is lowered due to problems such as the surface exposure of the core component A, and the poly-13-1245821 of the sheath component B is lost. 5. Description of the invention (12) Compound characteristics. On the one hand, a composite fiber with a composite ratio of sheath component B exceeding 10% by mass is less desirable due to the loss of the polymer characteristics of core component A. In the present invention, for example, a dyeable polymer is used as core component A to make the core The interval between the protruding portions of the component A is less than 1 · 5 // m. Using a dyeable polymer and a low refractive index ethylene-vinyl alcohol copolymer as the sheath component B, it can have a clear color development, Redness, etc. When these fibers are used in sportswear materials, they must not only have color development, but also have gloss. Generally, fibers with gloss have poor color development. Conversely, if they have color development, it is not easy to have gloss at the same time. Here, in the present invention, the composite component and the shape of the cut surface are made into a specific substance, whereby fibers with clear color development and luster can be obtained. In order to make the luster, a flat surface with more light reflection is more reasonable It is more effective to think or maintain the shape of a flat surface with a slight irregularity. This type of cutting surface, such as a triangular or flat cutting fiber, is most ideal. The thickness of the fiber in the present invention can be any thickness without any particular limitation, but In order to obtain fibers with excellent color development, gloss, appearance, and touch, the fiber fineness of the composite fiber is preferably 0.3 to 11 dtex. Moreover, not only long-fiber short fibers can also have the effects of the present invention. The method for producing the composite fiber of the present invention is not particularly limited, as long as a composite fiber conforming to the requirements of the present invention can be produced. When a composite spinning device is used to introduce a composite stream of a sheath component B and a core component A polymer into a nozzle inlet, The core component A passes through a manifold provided with the same number of fine holes as the protruding portion of the core component A on the circumference, and the sheath component B covers all the core component A passing through each fine hole, and at the same time faces the nozzle introduction port. Into the center of the composite flow, melt and spit out through the spinning nozzle -14-1245821 V. Description of the invention (13) Manufacturing. At this time, if a fine hole is provided in the middle of the shunt plate, a fiber with a composite cut surface as shown in Fig. 2 can be obtained, and when a fine hole is not provided in the middle, a fiber with a composite cut surface as shown in Fig. 1 can be obtained. The spinning and stretching methods include, for example, a method of stretching at a low speed and a medium speed after melt-spinning, a method of direct spinning at a high speed, and a method such as stretching and false drawing at the same time or subsequent to spinning. Any method may be adopted. In the present invention, it is desirable that the core component A contains inorganic fine particles. In this case, the primary average particle diameter of the more preferable inorganic fine particles is 0.01 to 5.0 // m, and more preferably 0.03 to 3.0 // m. If the primary average particle size of the inorganic fine particles is less than 0. 0 1 μm, the temperature of the heating zone to be stretched, the running speed of the yarn, and the tension related to the running yarn will change slightly, and the composite fiber will have curls and fluff. , Fineness spots and so on. On the other hand, if the primary average particle diameter of the inorganic fine particles exceeds 3.0 // m, the poor ductility of the fiber results in poor silk-making properties, and a phenomenon such as wire breakage may occur during the production of the composite fiber. Here, the primary average particle diameter of the inorganic fine particles refers to radon when measured by a centrifugal precipitation method. A more preferable content of the inorganic fine particles is about 0.05 to 10% by mass of the core component A, and more preferably 0.3 to 5.0% by mass. If the content of the inorganic fine particles is less than 0.1% by mass, as long as there is a slight change in the temperature of the heating zone to be stretched, the running speed of the yarn, and the tension related to the operation of the yarn, curling and fluff will occur in the resulting composite fiber. , Fineness spots, etc. On the other hand, if the content of the inorganic fine particles exceeds 10.0 mass. /. In the process of fiber extension, the inorganic particles will cause excessive resistance between the running yarn and the air, and curling and broken wires will cause the project to be unstable. In addition, in the core component A of the present invention, the primary average particle diameter of the inorganic fine particles (" m) -15-1245821 5. The invention description (14) and the product (Y) of the content (% by mass) in the polymer can meet 0 · 01 s 3.0 is ideal. If the accumulation is less than 0.01, the composite fiber will have curls and fluff, fineness spots, etc., and the engineering is not good, and the fiber is not easy to be used for clothing because it has many unstretched parts. If the accumulation is more than 3.0, the phenomenon of curling and wire breakage in fiberization engineering is not good. The type of the inorganic fine particles is not limited, and any inorganic fine particles that do not degrade the fiber-forming polyester and have good stability can be used. Representative examples of the inorganic fine particles that can be effectively used in the present invention include silicon dioxide, aluminum oxide, calcium carbonate, titanium oxide, and barium sulfate. These inorganic fine particles can be used alone or in combination of two or more. When two or more types are used in combination, the sum of the product of the particle size (al, a2, ... an) and the content (bl, b2, ... bn) of each inorganic particle must meet the above range. That is, Υ of Y = alxbl + a2xb2 +. · Ιηχΐ3η must meet the above range. The method for adding the inorganic fine particles to the core component A is not particularly limited, and the inorganic fine particles may be uniformly mixed and then added to the core component A at any stage before the core component A is melt-spun. For example, the inorganic fine particles are added at any point in the polymerization process of the core component a, or the inorganic fine particles are added after the particles are produced after the polycondensation is completed, or the inorganic fine particles are made at a stage before the core component A is spun from the spinning tap. Any method such as homogeneous melt mixing may be used. The fiber of the present invention produced by the above method can be used as various fiber aggregates (fiber structures). The fiber aggregate herein may be a woven fabric or a non-woven fabric composed of the fibers of the present invention, or a woven fabric or a non-woven fabric composed of the fibers of the present invention, such as natural fibers, chemical fibers, synthetic fibers, and the like. Interactive woven fabrics formed by fibers, or fabrics used for blended yarns, blended nonwovens, etc., this -16-1245821 V. Description of the invention (15) The proportion of the invention's fibers in such fabrics and nonwovens is greater than 10%. Mass%, and more than 30 mass% is more desirable. The main purpose of the fiber of the present invention is to use long fibers alone or in part to make a fabric, which can be used as a material for clothing with good appearance and touch. On the other hand, staple fibers are used for clothing fibers, dry-type nonwovens, and wet-type non-wovens. They are used not only for clothing but also for non-clothing applications such as various living materials and industrial materials. [Examples] The present invention will be described more specifically with examples below, but the present invention is not limited to these examples. Intrinsic viscosity of polymer: Determine the intrinsic viscosity of polyester by using an equal mass mixed solvent of phenol and tetrachloroethane in a 30 ° C constant temperature bath and using an Ubilod type translucent viscosity agent. The intrinsic viscosity of the saponified ethylene-vinyl acetate copolymer was determined using 30% phenol at 30 ° C. Brightness and gloss of the hair: 10 judges evaluated the functionality of the cloth dyed under certain dyeing conditions. As a result, two points were very excellent, one point was excellent, and zero point was defective. 〇: The total number of points is more than 15 points △: The total number of points is 8 to 14 points X: The adhesion of each polymer of the composite fiber is less than 7 points: The fibers of 2 4 to 36 are made into 500-1 000 T / m twisted yarn, the yarn was cut in this state, and the delamination state of the fiber at the cut surface was observed with an electron microscope magnification of 500 times. The cut-off point is 10 points. -17- 1245821 V. Description of Invention (16) Evaluation. ◎: Degree of delamination is less than 10% 〇: Degree of delamination is 10% to 20% △: Degree of delamination is 20% to 50% X: Degree of delamination is more than 50% Fiber strength: Measured based on JISL 1013. Fibrosis engineering property: The number of fluffs and the number of broken wires per ton are evaluated. ◎: The total number of fluff and broken wires is less than 1 per ton. 0: The total number of fluff and broken wires is 1 to 2 per ton. △: The total number of fluff and broken wires is 2 to 5 per ton. X: More than 5 per ton. Dyeability ... The dyeing rate when the tube-shaped material is dyed under the following conditions: Foron Navy S2GL 2% omf Di sper-TL 1 g / 1 acetic acid (50%) 1 cc / 1 liquid ratio 1:50 120 ° C x40-minute total evaluation: Observe the items of fibrosis engineering, delamination resistance, and dyeability in a comprehensive way, and evaluate the following standards. ◎: Each item is ◎ 〇: Each item is ○ X and △ to X are shown to be equivalent to the worst evaluation result of each item. Example 1 Nylon 6 (8? 値 = 12.7, 101381〇 manufactured by Ube Kosan Co., Ltd.) was used as the sheath component B, and polyethylene terephthalate (SP 値 = 10.7 -18-1245821) was used. 2) Saponification degree of 9 9 ° /. After saponification of the above ethylene-vinyl acetate copolymer, the washing was repeated with excess pure water containing a small amount of acetic acid, and then the washing was repeated with excess pure water to polymerize. The content of potassium, sodium ions, magnesium, and calcium ions in the product are all less than 10 ppm. After the water in the polymer is separated by a dehydrator, the vacuum drying is performed at a temperature lower than 10 (TC) to prepare A polymer with intrinsic viscosity [η] = 1.05 dl / g (SP 値 = 17.2) was used as the polymer for sheath component B. On the other hand, tetraisopropyl titanate was used as the polymer Catalyst was added and polybutylene terephthalate (1.7 mol /% sodium thioisophthalate formed by copolymerization) was formed to copolymerize the titanium metal atom content in the polymer The polymer was 35 ppm, and was polymerized by a conventional method to obtain a polymer having inherent viscosity [η] = 0.85 dl / g as a core component A. The polymer was melt-spun under the conditions of a composite ratio (mass ratio) of sheath component B and core component A of 50:50, and a spinning temperature of 26 (TC and a winding speed of 3,500 m / min). A composite fiber (8 3 dtex / 24 fiber) with a cut shape as shown in Fig. 3 is obtained. The core component a of this composite fiber has 50 protruding portions, and the average interval between adjacent protruding portions is 0.3 5 // m. The outer perimeter (L2) of the core component A and the outer perimeter of the composite fiber (the ratio of Ld 2 / Ι ^ = 4.5 (X / (: = 9 · 0), the strength is 3.1 N / dtex. Then 800 The actual fabric of T / M is used to make fabrics. The fabrics are dyed using the cross-linking treatment conditions and dyeing conditions shown below using a general liquid dyeing machine, and then dried by conventional methods to complete the process. The dyed fabrics have Good hair color, sharpness and excellent gloss, no core-sheath interface delamination phenomenon at all. It also has good appearance and touch. The results are shown in Table 4-22-1245821 V. Description of the invention (21). Cross-linking treatment conditions Treatment agent: 1,1,9,9, -Diethylenedihydroxynonane 10% omf Dodecylsulfonic acid Sodium 0.5g / l maleic acid lg / 1 Liquid ratio: 1: 5 0 Temperature: 115 ° C x 40 minutes Dyeing conditions Dye: Dianix Red BN-SE (CI Disperse Red 127) Dispersion aid: DisperTL (Mingcheng Chemical Industry Company) (Manufactured) PH adjuster: ammonium sulfate acetic acid (48%) liquid ratio: 1: 50 0 temperature: 115 ° C x 40 minutes reduction rinsing hydrogenated hydrogen sulfite lg / 1 amiragin (first industrial pharmaceutical) lg / 1 NaOH lg / 1 liquid ratio: 1: 3 0 temperature: 80 ° C xl20 minutes 5% omf lg / 1 lg / 1 lg / 1 -23-1245821 V. Description of the invention (22) Table 3
:複合纖維 扁平度 CO CN cn c\j CsJ cn CNi S 寸 04 :· I cn CO <N 寸 cvi I I I I I I I (L2/LD/C 〇· CD 寸 ai 寸 cn CO cd cn <b 5 〇0 CD to in o CO 寸· 寸 ai C\J ai 0.96 I 0.96 I - 0.98 ! CN 0.96 0.96 L2 八·1 in 卜 r- 寸· n CO cn CO 寸 寸· <ri 00 cvi in r- cn CO 寸 I 0.48 I I 0.48 I I 0.55 I I 0.49 | I 〇：6〇 I I 0.48 | I 0.48 角度 (R° ) !80 〜90| 80 〜90| |80 〜9〇| 80 〜90| !80 〜90| |80 〜90| |80 〜90| |80 〜9〇| 丨75〜90| |80 〜90| |80〜90| 80 〜90 I I I I I I I 突出部 i間隔⑴ 1 0.35 | | 0.35 | [0.64 | I 0.65 | Ι〇_·61 1 I 0.61 I | 0.65 | r^ 〇· I —0.72. I CD 〇 I 0.35 | 里 I I I I I I I 突出部 分個數 g g o in |第3圖，30 I g s o o n o o 〇 〇 切面 形狀· 第3圖」 | 0.5 :第3丽] | 0.5萬3圖I 第3圖 第3圖 第4圖i 第5圖 I第3圖 第3圖 网3圖 第9圖 障9圖 第9圖I 第9圖 第9圖 第9圖 |第9圖j 複合 比率 1 (C) in Ο L〇 CO LO o in 〇· in Ο LO o in in to ο ΙΟ ο in d in 〇 m 〇· ιο in 〇 < <R HV 共聚合種~ 類/共聚重· SIP/1.7 | SIP/1.7 | 一/一 I IPA/4.0 | IPA/4.0 | ΙΡΑ/4.0 I I 一I | SlP/1.7 | I SIPX1.7 I ΓΞΖΞΊ I 1PA/4.0 | —/一 S1P/1.7 ΓΞΖΞΊ 丨一/一 ! 丨一_ I \ I I IPA/4.0 I -/一 is W 種類 SIPcoPBTl SIPcoPETl PET | IPAcoPETl IPAcoPETl IPAcoPETl CO i SIPcoPBTl I SIPcoPBTl a a | IPAcoPETl m I SIPcoPBTl L_pet J 「—PET I CO Z CL Q. I IPAcoPETl I PET ω <R 皂化度 1 (%) σ> σ) CD σ> <T> σ> cn cn cn 05 cn cn cn cn <D cn CJ5 cn σι σ> 05 σ> cn cn cn cn CD 05 cn cn cn CD cn 乙烯共聚 量(莫耳％) 寸 寸 CNi n CO in 寸 言 04 Cl CO in 二 m CM Cl 寸 LO CO 卜 CO cn OJ CsJ 寸 AJ in CD ao CD O ^ - HKfc褰1£鏃：dd , SUNO瀣 frn擀諒鏃^«rEZg^fr:::擀sp}ti-s : IHdsdIS 91105: 9Z, ggSHJL 瀣in 擀諒酴踩«rEZl^frn 擀ffips-ς: ladsdls -24- 1245821 五、發明說明（23) 表4: Flatness of composite fiber CO CN cn c \ j CsJ cn CNi S inch 04: · I cn CO < N inch cvi IIIIIII (L2 / LD / C 〇 · CD inch ai inch cn CO cd cn < b 5 〇0 CD to in o CO inch · inch ai C \ J ai 0.96 I 0.96 I-0.98! CN 0.96 0.96 L2 · 1 in r r- inch · n CO cn CO inch · < ri 00 cvi in r- cn CO inch I 0.48 II 0.48 II 0.55 II 0.49 | I 〇: 6〇 II 0.48 | I 0.48 angle (R °)! 80 to 90 | 80 to 90 | | 80 to 9〇 | 80 to 90 |! 80 to 90 | | 80 ～ 90 | | 80 ～ 90 | | 80 ～ 9〇 | 丨 75 ～ 90 | | 80 ～ 90 | | 80 ～ 90 | 80 ～ 90 IIIIIII protrusion i interval ⑴ 1 0.35 | | 0.35 | [0.64 | I 0.65 | Ι〇_ · 61 1 I 0.61 I | 0.65 | r ^ 〇 · I —0.72. I CD 〇I 0.35 | Here the number of IIIIIII protruding parts ggo in | Figure 3, 30 I gsoonoo 〇〇 Cut shape · Figure 3 "0.5: 3rd Li] | 0.5 million 3 pictures I 3 pictures 3 pictures 4 i pictures 5 pictures 3 pictures 3 pictures 9 pictures 9 pictures 9 pictures 9 pictures 9 pictures Fig. 9 Fig. 9 | Fig. 9 j Composite ratio 1 (C) in Ο L〇CO LO o in 〇 · in Ο LO o in in ο Ι ο in d in 〇m 〇 · ιο in 〇 < < R HV copolymerized species ~ class / copolymer weight · SIP / 1.7 | SIP / 1.7 | Mon / I I IPA / 4.0 | IPA / 4.0 | ΙΡΑ / 4.0 II One I | SlP / 1.7 | I SIPX1.7 I ΓΞZΞΊ I 1PA / 4.0 | — / One S1P / 1.7 ΓΞZΞΊ 丨 One / One! 丨 One_ I \ II IPA / 4.0 I-/ One is W Type SIPcoPBTl SIPcoPETl PET | IPAcoPETl IPAcoPETl IPAcoPETl CO i SIPcoPBTl I SIPcoPBTl aa | IPAcoPETl m I SIPcoPBTl L_pet J 「—PET I CO Z CL Q. I IPAcoPETl I PET ω < R Saponification degree 1 (%) σ > σ) CD σ > lt σ > cn cn cn 05 cn cn cn cn < D cn CJ5 cn σι σ > 05 σ > cn cn cn cn CD 05 cn cn cn CD cn Ethylene copolymerization (mole%) inch CNi n CO in inch 04 Cl CO in 2m CM Cl inch LO CO bl CO cn OJ CsJ inch AJ in CD ao CD O ^-HKfc 褰 1 £ 镞: dd, SUNO 瀣 frn roll out 镞 ^ «rEZg ^ fr ::: 擀 sp} ti-s : IHdsdIS 91105: 9Z, ggSHJL 瀣 in 酴 forgive me 酴 rezl ^ frn ffips-ς: ladsdls -24- 1245821 V. Description of the invention (23) Table 4
評估結果 纖維化 工程性 耐層離性 觸感評估 總合評估 實例11 ◎ ◎ 鮮明性、光澤感良好。具有 微濕乾燥感的外觀、觸感。 ◎ 12 〇 ◎ // 〇〜◎ 13 〇〜© ◎ // 〇〜◎ 14 ◎ 〇〜◎ " 〇〜◎ 15 ◎ 〇〜◎ " 〇〜◎ 16 ◎ 〇〜◎ " 〇〜◎ 17 ◎ ◎ // ◎ 18 〇〜© ◎ // 〇〜◎ 19 〇〜◎ ◎ // 〇〜◎ 20 ◎ 〇〜◎ 具良好外觀、觸感之濕式不織布 〇〜◎ 21 〇〜◎ 〇〜◎ 鮮明性、光澤感良好。具有_ 微濕乾燥感的外觀、觸感 〇〜◎ 22 ◎ 〇〜◎ " 〇〜◎ 比較例4 〇〜◎， △〜X 雖鮮明性、外觀觸感良好、 惟因層離導致嚴重損害無 法做爲外衣等實用等級。 △〜X 5 〇〜◎ X // X 6 〇〜◎ △〜X η △〜X 7 ◎ △〜X " △〜X 8 〇〜@ △〜X 界面層離嚴重、品質差。 △〜X 9 〇〜◎ X 同比較例4 X 10 ◎ X // X 實例12〜17 除了芯成分A、複合比率、突出部分個數更改爲表3 表示者之外，進行和實例Π相同的步驟。耐層離性評 估結果及外觀、觸感i平估結果如表4所示。無論任一製 品其纖維化工程性良好，具有優異的耐層離性和良好的 外觀、觸感。實例1 8，1 9 除了切面形狀更改爲第4、5圖所示者之外，進行和 實例1 1相同的步驟。無論任一製品皆具有優異的耐層 離性和良好的外觀、觸感。實例20 -25- 1245821 五、發明說明（24) 除了以聚丙烯作爲芯成分A之外，和實例i〗相同地 製作複合纖維。將纖維切成5 mm，根據常法造紙，並使 其通過1 1 0 t：的滾筒輪壓機製作濕式不織布。製得加工 工程性佳、質地、品質良好的不織布。 實例21，22 除了將鞘成分B的乙烯的共聚合量更改爲表3所示者 之外進行和實例1 1相同的步驟。無論任一製品皆具有 優異的耐層離性和良好的外觀、觸感。 比較例4 - 7 除了芯成分A及切面形狀、芯成分A的突起個數更改 爲表3表示者之外進行和實例1 1相同的步驟。無論任 一製品皆具有良好的外觀、觸感，惟因芯鞘界面的層離 導致嚴重的損害，爲品質不佳的製品，不符合實用性的 等級。 比較例8 以聚丙烯作爲芯成分A，和實例20同樣地將纖維切 成5 mm，製作濕式不織布，惟在加工工程上多發生芯鞘 界面層離，明顯爲劣質品。 比較例9，1 〇 除了將鞘成分B的乙烯的共聚合量更改爲表3所示者 之外進行和實例1 1相同的步驟。無論任一製品皆因芯 鞘界面的層離導致嚴重的損害，爲低品質的製品。 實例23 將實例U中製作的乙烯-醋酸乙烯共聚物皂化物作爲 -26- 1245821Evaluation results Fibrosis Engineering resistance Delamination resistance Tactile evaluation Total evaluation Example 11 ◎ ◎ Good sharpness and gloss. Has a slightly wet, dry appearance and touch. ◎ 12 〇 ◎ // 〇〜 ◎ 13 〇 ~ © ◎ // 〇〜 ◎ 14 ◎ 〇〜 ◎ " 〇〜 ◎ 15 ◎ 〇〜 ◎ " 〇〜 ◎ 16 ◎ 〇〜 ◎ " 〇〜 ◎ 17 ◎ // ◎ 18 〇 ～ © ◎ // 〇〜 ◎ 19 〇 ～ ◎ ◎ // 〇〜 ◎ 20 ◎ 〇 ～ ◎ Wet type nonwoven fabric with good appearance and touch 〇〜 ◎ 21 〇 ～ ◎ 〇〜 ◎ Brightness and gloss. Appearance and feel with _ slightly wet and dry feel ～～ 22 ◎ ○ ～ ◎ " 〇 ～ ◎ Comparative Example 4 〇 ～ ◎, △ ～ X Although sharp, the appearance and touch are good, but serious damage is caused by delamination Can not be used as a practical level such as outerwear. △ ~ X 5 〇 ~ ◎ X // X 6 〇 ~ ◎ △ ~ X η △ ~ X 7 ◎ △ ~ X " △ ~ X 8 〇 ~ @ △ ~ X The interface layer is severe and the quality is poor. △ ~ X 9 〇 ~ ◎ X Same as Comparative Example 4 X 10 ◎ X // X Examples 12 to 17 Except that the core component A, the compound ratio, and the number of protruding parts are changed to those shown in Table 3, the same procedure as in Example Π is performed. step. Table 4 shows the evaluation results of delamination resistance, and the evaluation results of appearance and touch. Either product has good fiberization engineering properties, excellent delamination resistance, and good appearance and touch. Examples 1 and 19 were carried out in the same manner as in Example 1 except that the shape of the cut surface was changed to those shown in Figs. 4 and 5. Either product has excellent resistance to delamination and good appearance and touch. Example 20 -25-1245821 V. Description of the invention (24) A composite fiber was produced in the same manner as in Example i except that polypropylene was used as the core component A. The fiber was cut into 5 mm, and paper was made according to a conventional method, and passed through a roller press of 1 10 t: to make a wet non-woven fabric. Processed non-woven fabric with good engineering, texture and good quality. Examples 21 and 22 were carried out in the same manner as in Example 11 except that the copolymerization amount of ethylene in sheath component B was changed to that shown in Table 3. Either product has excellent delamination resistance and good appearance and touch. Comparative Examples 4-7 The same procedure as in Example 11 was performed except that the core component A, the cut surface shape, and the number of protrusions of the core component A were changed to those shown in Table 3. Either product has a good appearance and feel, but it is seriously damaged due to the delamination of the core-sheath interface. It is a poor-quality product and does not meet the practical level. In Comparative Example 8, polypropylene was used as the core component A, and fibers were cut into 5 mm in the same manner as in Example 20 to produce a wet-type non-woven fabric. However, core-sheath interface delamination occurred in the processing process, which was obviously inferior. In Comparative Example 9, 10, the same procedure as in Example 11 was performed except that the copolymerization amount of ethylene in sheath component B was changed to that shown in Table 3. Either product is seriously damaged due to the delamination of the core-sheath interface and is a low-quality product. Example 23: The ethylene-vinyl acetate copolymer saponified in Example U was used as -26-1245821.
五、發明說明（25 )V. Description of the invention (25)
革肖成刀B用的聚合物，冋樣地’使貫例1 1中製作的聚 對苯二甲酸丁二醇酯（由佔全酸成分的1·7莫耳％的％硫 代間苯二甲酸鈉經過共聚形成）含有特定量的表5表示 之無機微粒，以此化合物作爲芯成分Α用之聚合物，在 鞘成分B和芯成分A的複合比率（質量比率）5 〇 : 5 0的條 件’以肪絲溫度260C、捲取速度3500 m/分的條件進 行熔融複合紡絲，製得如第6圖所示切面形狀的複合纖 維（8 3 dtex/24纖維）。惟此複合纖維的芯成分A(L/D = 6.〇) 的突出部分有50個，鄰接突出部分間的平均間隔爲0.33 # m 。芯成分A的總外周長（L2)和複合纖維的外周長（1^)的 比（L2/L!)爲 5.0(X/C=10.0)，強度爲 3.1 N/dtex。其次進 行8 00 T/Μ的實拈，製作織物，和實例1 1同樣地使製 得的織物進行交聯處理及染色，之後以常法進行乾燥完 成工程。染色後的織物具有良好的發色、鮮明性及優異 的光澤感，完全不發生芯鞘界面層離現象。且具有良好 的外觀、觸感。結果如表6所示。The polymer used for the leather knife B was made in the same way as the polybutylene terephthalate produced in Example 11 (consisting of 1. Formed by copolymerization of sodium diformate) Contains a specific amount of inorganic fine particles shown in Table 5, and uses the compound as a core component A. The compound ratio (mass ratio) of sheath component B and core component A is 5 0: 50. Condition 'The melt-composite spinning was performed under the conditions of a fat yarn temperature of 260C and a winding speed of 3500 m / min, and a composite fiber (8 3 dtex / 24 fiber) having a cut shape as shown in Fig. 6 was obtained. However, there are 50 protruding portions of the core component A (L / D = 6.〇) of the composite fiber, and the average interval between adjacent protruding portions is 0.33 # m. The ratio (L2 / L!) Of the total outer perimeter (L2) of the core component A to the outer perimeter (1 ^) of the composite fiber was 5.0 (X / C = 10.0), and the strength was 3.1 N / dtex. Next, 8000 T / M was used to fabricate the fabric, and the resulting fabric was subjected to a cross-linking treatment and dyeing in the same manner as in Example 11 and then dried in a conventional manner to complete the process. The dyed fabric has good color development, sharpness, and excellent gloss, and the core-sheath interface delamination does not occur at all. And has a good appearance and touch. The results are shown in Table 6.
-27- 1245821 五、發明說明（28) 除了以聚丙烯作爲芯成分A之外，和實例2 3相同地 製作複合纖維。將纖維切成5 mm，根據常法造紙，並使 其通過1 1 0°C的滾筒輪壓機製作濕式不織布。製得加工 工程性佳、質地、品質良好的不織布。 實例3 3，3 4 除了將鞘成分B的乙烯的共聚合量更改爲表5所示者 之外進行和實例2 3相同的步驟。無論任一製品皆具有 優異的耐層離性和良好的外觀、觸感。 比較倒1 1〜13 除了芯成分A及切面形狀更改爲第9圖表示的芯鞘型 之外進行和實例2 3相同的步驟。無論任一製品皆具有 良好的外觀、觸感，惟因芯鞘界面的層離導致嚴重的損 害，爲品質不佳的製品，不符合實用性的等級。 比較例1 4 除了將複合比率及島數更改爲表5表示者之外進行和 實例2 3相同的步驟。無論任一製品其纖維化工程性、 耐層離性皆不佳。 比較例1 5 以聚丙烯作爲芯成分A，和實例2 3同樣地將纖維切 成5mm，製作濕式不織布，惟在加工工程上多發生芯鞘 界面層離，明顯爲劣質品。 比較例1 6，1 7 除了將鞘成分B約乙烯的共聚合量更改爲表5所示者 之外進行和實例2 3相同的步驟。無論任一製品皆因芯 30- 1245821 五、發明說明（μ) 鞘界面的層離導致嚴重的損害，爲低品質的 【應用在產業上的領域】 本發明的複合纖維具有優異的加工工程性 的耐層離性，且染色物的侵鈾性等優異，可 好外觀、觸感的衣料用素材。不僅爲衣料用 各種生活資材、產業資材等非衣料用途。又 合成纖維所無的良好親水性，可製得出發色 良好具有柔軟且類似天然纖維般的外觀、觸 性優異的複合纖維構成之纖維製品。 製品。 及心銷成分 作爲具有良 ，亦適用於 ，具有以前 性、光澤感 感和耐層離-27- 1245821 V. Explanation of the invention (28) A composite fiber was produced in the same manner as in Example 2 3 except that polypropylene was used as the core component A. The fibers were cut into 5 mm, paper was made according to a conventional method, and passed through a roller press at 110 ° C to make a wet nonwoven fabric. Processed non-woven fabric with good engineering, texture and good quality. Examples 3 and 3 4 The same procedure as in Example 2 3 was performed except that the copolymerization amount of ethylene in sheath component B was changed to that shown in Table 5. Either product has excellent delamination resistance and good appearance and touch. Comparative steps 1 to 13 The same procedure as in Example 2 3 was performed except that the core component A and the cut surface shape were changed to the core sheath type shown in FIG. 9. Either product has a good appearance and feel, but it is seriously damaged due to the delamination of the core-sheath interface. It is a poor-quality product and does not meet the practical level. Comparative Example 1 4 The same procedure as in Example 2 3 was performed except that the compound ratio and the number of islands were changed to those shown in Table 5. Regardless of any product, its fiberization engineering property and delamination resistance are not good. In Comparative Example 15, polypropylene was used as the core component A, and fibers were cut into 5 mm in the same manner as in Example 23 to produce a wet-type non-woven fabric. However, core-sheath interface delamination occurred in the processing process, which was obviously inferior. Comparative Examples 16 and 17 The same procedures as in Example 2 3 were performed except that the copolymerization amount of sheath component B and ethylene was changed to that shown in Table 5. No matter any product, the core 30-1245821 V. Description of the invention (μ) The delamination of the sheath interface causes serious damage, which is of low quality. [Application in the field of industry] The composite fiber of the present invention has excellent processability. It has excellent delamination resistance and excellent uranium invasion properties for dyed materials. Not only for clothing, but also for various non-clothing applications such as living materials and industrial materials. In addition, the synthetic fiber has good hydrophilicity, and can be made into a fiber product that has a good starting color, has a soft, natural fiber-like appearance, and excellent touch properties. product. And the heart pin component has good properties, and is also suitable for use. It has previous properties, shiny feeling and resistance to delamination.